Alkynyloxy-phenyl derivatives

ABSTRACT

Alkynyl, benzyl or phenyl, ethers and esters which are ring substituted with an oxy or a thio aliphatic chain. These ethers and esters are useful in killing and preventing the proliferation of insects by upsetting their hormonal balance.

United States Patent Chodnekar et al.

ALKYNYLOXY-PHENYL DERIVATIVES Inventors: Madhukar Subraya Chodnekar,

Basel; Albert Pfiffner, Pfaffhausen; Norbert Rigassi, Arlesheim; Ulrich Schwieter, Reinach; Milos Suchy, Basel, all of Switzerland Hoffman-La Roche Inc., Nutley, NJ.

Filed: Dec. 4, 1972 Appl. No.: 312,074

Related U.S. Application Data Division of Ser. No. l23,060, March 10, I971 Pat. No. 3,718,686.

Assignee:

Foreign Application Priority Data Mar. 25, I970 Switzerland 462l/70 U.S. Cl. 260/613 D; 260/240 H Apr. 29, 1975 Primary Examiner-Bernard Helfin Attorney, Agent, or FirmSamuel L. Welt; Jon S. Saxe; Richard A. Gaither [57] ABSTRACT Alkynyl, benzyl or phenyl, ethers and esters which are ring substituted with an oxy or a thio aliphatic chain. These ethers and esters are useful in killing and preventing the proliferation of insects by upsetting their hormonal balance.

15 Claims, No Drawings 1 A 2 ALKYNYLOXY-PHENYL DERIVATIVES R R l l a 3 CROSS REFERENCE TO RELATED D APPLICATIONS Hal This application is a division of the copending appli- A l E IV cation, Ser. No. 123,060, US. Pat. No. 3,7l8,686 filed R R Mar. l0, I97], entitled Alkynyloxy-Phenyl Derivatives", as filed and now US. Pat. No. 3,718,686.

SUMMARY OF THE MENTION wherein R,, R2, R R4, R,,, A, B, c, D, E, F, Hal, m,

In accordance with this invention, it has been found n and p are as abo that compounds of the formula: with a compound of the formula:

B l i i ii wherein R R and R are methyl or ethyl; R and R, i Y are hydrogen or methyl; R is lower alkynyl; A, B, C, D, E and F are individually hydrogen or A and M Z B taken together form a carbon to carbon bond or an oxygen bridge, C and D taken together form a carbon to carbon bond, and E and F taken together x form a carbon to carbon bond; Z is oxygen or sul- 3 fur; Y and Y are hydrogen, halogen, lower alkyl or lower y: X is y -e or wherein R,,, x, Y, Y' and Z are as above and M' is and i and P are integers of from 0 t0 1, with at an alkali metal or, where Z is oxygen, an alkali least one of m, n and p being l; with the proviso meta] or h d that when m and n are 0, E and F are individually Th cumpounds of formula I wherein X is hydrogen, or taken together form a carbon to carbon bond or an oxygen bridge;

upset the hormone balance of pests such as insects to l prevent them from growing and reproducing.

The compounds of formula I are prepared by reactare further prepared by reacting a compound of the ing a compound of the formula: formula:

wherein R R R R R5, A, B. C. wherein i. 2, 3 4. 5. X, m, n and p are as above and M is an alkali metal m, n and p are as above and R, is hydrogen, lower or, where X is oxygen, an alkali metal or hydrogen; alkyl or aralkyl; with an alkynyl halide of the formula: with an alcohol of the formula:

R,,-Hal Ill R OH vii wherein R,- is as above and Hal is a halogen. wherein R is as above. The compounds of formula I are also prepared by re- In the case where, in the compound of formula I, A

acting a halide of the formula: and B taken together form a carbon to carbon bond,

this compound can be epoxidized to a compound of formula I wherein A and B taken together form an oxygen bridge.

DESCRIPTION OF THE PREFERRED EMBODIMENT As used throughout this application, the term lower alkyl comprehends both straight-chain and branchedchain, saturated alkyl hydrocarbon groups havng from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc, As used herein, the term lower alkoxy comprehends loweralkyloxy groups wherein a lower alkyl is defined as above, such as methoxy, ethoxy propoxy, etc. Similarly, as used herein, the term lower alkynyl includes straight-chain and branched-chain, acetylenically unsaturated hydro carbon groups having from 2 to 6 carbon atoms, such as ethynyl, propargyl. butynyl, etc. As also used herein, the term "halogenl or "halo comprehends, when not expressly stated otherwise, all four halogens, i.e. fluorine, chlorine. bromine and iodine. As further used herein, the term alkali metal comprehends the alkali metals of the first group of the periodic chart, such as sodium and potas sium. As still further used herein, the term aralkyl comprehends aryl lower alkyl groups wherein aryl comprehends mono-nuclear aromatic hydrocarbons, such as phenyl, tolyl, etc., which can be substituted or unsubstituted in one or more positions, and polynuclear aromatic groups, such as naphthyl, phcnanthyl, etc., which can also be substituted or unsubstituted in one or more positions. with a nitro, halo, lower alkyl or lower alkoxy substituent, and wherein lower alkyl is as defined above. The preferred aralkyl group is benzene.

The compounds of formula I are useful in the control of and in combatting invertebrate animals, such as arthropods and nematodes. The compounds of formula I are especially useful against insects, particularly Tenebrio molimr, Tineola biselliella, Carpocapsu pumonella, Leptinolursa decent/Enema, Calanclm granaria, Dysdercus cingulatus and Ephestia kiihniella.

In contrast to most of the known pest-control agents which kill, disable or repell the pests by acting as contact-poisons and feed-poisons. the compounds of formula I above prevent maturation and proliferation of these pests by interfering with their hormonal system. In insects, for example, the transformation to the imago, the laying of viable eggs and the developement of laid normal eggs is distrubed. Furthermore, the sequence of generations is interrupted and the insects are indirectly killed.

The compounds of formula I above are practically non-toxic to vertebrates. The toxicity of the com pounds of formula I is greater than, 1,000 mg/kg body weight. Moreover. these compounds are readily degraded and the risk of accumulation is therefore excluded, Therefore, these compounds can be used with out fear of danger in the control of pests in animals; plants; foods; and textiles.

Generally, in controlling invertebrate animals, the compounds of formula I are applied to the material to be protected. e.g. foodstuffs, feeds, textiles, plants, in concentrations of from about l to 10 gm/cm" of the material to be protected. Generally, it is preferred to utilize the compounds of formula I above in a composition with a suitable inert carrier. Any conventional inert carrier can be utilized.

The compounds of formula I can, for example, be used in the form of emulsions, suspensions, dusting agents, solutions or aerosols. In special cases, the materials to be protected (e.g., foodstuffs, seeds, textiles and the like) can also be directly impregnated with the appropriate compound or with a solution thereof. Moreover, the compounds can also be used in a form which only releases them by the action of external influences (e.g., contact with moisture) or in the animal body itself. It is also possible to use the compounds in admixture with other known pesticides.

The compounds of formula I above can be used as solutions suitable for spraying on the material to be protected which can be prepared by dissolving or dispersing these compounds in a solvent such as mineral oil fractions; cold tar oils, oils of vegetable or animal ori gins; hydrocarbons such as napthalenes', ketones such as methyl ethyl ketone', or chlorinated hydrocarbons such as tetrachloroethylene, tetrachlorobenzene, and the like. Such sprays suitably have a concentration of the compound of formula I of 0.01 to 5% by weight, with a concentration of 0.1% being preferred. The compounds of formula I above can also be prepared in forms suitable for dilution with water to form aqueous liquids such as, for example, emulsion concentrates, pastes or powders. The compounds of formula 1 above can be combined with solid carriers for making, dusting or strewing powders as, for example, talc, kaolin, bentonite, calcium carbonate, calcium phosphate, etc. The compositions containing the compounds of formula I above can contain, if desired, emulsifiers, dispersing agents, wetting agents, or other active substances such as fungicides, bacteriacides, nematocides, fertilizers and the like. The materials which are to be protected act as bait for the insect. In this manner, the insect, by contacting the material impregnated with a compound of formula 1 above, also contacts the compound itself.

In accordance with this invention, representative examples of the preferred compounds of formula I are as follows:

I-[( l,5dimethylhexyl )oxy]-4-(propargyloxy )benzene; l-[(3-methyl-2-butenyl)oxy]-4-propargyloxybenzne; p-[( l ,S-dimethylhexyl )oxy l-a-propargyloxytoluene; p-[(3-methyl-2-butenyl)oxy]-a-propargyloxyloluene; p-[(l,S-dimethylhexyl)oxylbenzoic acid propargyl ester; p [(3,7-dimethyl-2,6octadienyl)oxylbenzoic propargyl ester; p-[(2,3-epoxy-3-methylbutyl)oxylbenzoic acid propargyl ester;

acid

p-[ 4,5-epoxyl ,5 -dimethylhexyl )oxy lbenzoic acid propargyl ester; p-[( l-ethyl-5-methyl4-heptenyl )oxy ]benzoic acid p-[(l,S-dimethylhexyl)oxy]benzoic acid propargyl ester; 4-[(1,S-dimethylhexyl)oxy]-o:-(propargyloxy)toluene; p-[(4,5-epoxy-l,S-dimethylhexyl)oxylbenzoic acid propargyl ester; p-[( 1,5-dimethylhexyl )oxy-lbenzoic acid-2-pentynyl ester;

p l,4,5-trimethylhexyl)oxylbenzoic acid propargyl ester;

p-H l,S-dimethylhexyl)thio]benzoic acid propargyl ester;

p-[(3,6,7-trimethylocta 2,6-dienyl)oxy]benzoic acid propargyl ester,

p-[(3,6,7-trimethyloctyl)oxylbenzoic acid propargyl ester;

4-[( l ,S-dimethylhexyl)oxy1-3-chlorobenzoic acid propargyl ester;

p-[( I ,S-dimethylhexyl)oxylvanillic acid propargyl ester;

3-methyl-4-[(3,7-dimethylocta-2,b-dienyl)oxylbenzoic acid propargyl ester;

3-bromo-4-[(6,7-dimethyl-2,o-octadienyl)oxy]-5- methoxybenzoic acid propargyl ester; and

4-[(3,7-dimethyl-2,o-octadienyl)oxy1-3.5 dimethoxy-benzoic acid propargyl ester.

Especially preferred are the compounds of formula I having the formula wherein R,, R R,-,, A, B, X, Y. Y' and Z are as above. Particularly preferred are the compounds of formula la wherein Z is oxygen, Y is hydrogen, and A and B individually are hydrogen or taken together form an oxy gen bridge. Quite particularly preferred are the following compounds of formula la:

l-[( l,S-dimethylhexyl)oxy]-4-propargyloxy benzene;

p-[(l,S-dimethylhexyl)oxylbenzoic acid propargyl ester;

4-[( l ,S-dimethylhexyl )oxy]-a(propargyloxy)toluene;

p-[(4,5-epoxy-l,5-dimethylhexyl)oxy]benzoic acidpropargyl ester; and p-[( l,4,5-trimethylhexyl)oxylbenzoic acid propargyl ester. Also especially preferred are the compounds of the formula I having the formula:

Further especially preferred compounds are the compounds of formula I wherein R,, R and/or R are methyl; R and/or R is hydrogen; 2 is oxygen, and/or Y and Y are hydrogen.

One method for preparing the compounds of formula I involves reacting, in a well known manner, a compound of formula II with the alkynyl halide of formula lll. This reaction is suitably conducted in an inert solvent and preferably in the presence of an aprotonic solvent. ln carrying out this reaction, any conventional inert organic solvent can be utilized, with benzene, tol uenc, dioxane, l,2-dimethoxymethane and tetrahydrofuran being preferred and tetrahydrofuran being espe cially preferred. in this reaction, any coventional apro tonic solvent may be utilized, with hexamethyl phosphoric acid triamide being preferred. In this reaction, temperature and pressure are not critical, and the reaction can be suitably carried out in a temperature range of 0C. to the boiling point of the reaction mixture. In a preferred embodiment of this reaction, the reaction is carried out at ca 70C., the reflux temperature of the especially preferred solvent.

Another method for preparing the compounds of formula l involves reacting, in a well known manner, the compounds of formulas IV and V. This reaction is also suitably carried out in an inert solvent, preferably in the presence of an aprotonic solvent. ln carrying out this reaction, any conventional inert organic solvent can be utilized, with benzene, toluene, dioxane, l,2- dimethoxymethane and tetrahydrofuran being preferred and tetrahydrofuran being especially preferred. In this reaction, any conventional aprotonic solvent may be utilized, with hexamethyl phosphoric acid triamide being preferred. In this reaction, temperature and pressure are not critical, and the reaction can be suitably carried out in a temperature range of 0C. to the boiling point of the reaction mixture. In a preferred embodiment of this reaction, as in the above reaction. the preferred temperature is ca 70C.

The reaction mixtures from the reactions of either a compound of formula II with a compound of formula III or a compound of the formula IV with a compound of formula V can be worked up in a conventional manner to obtain the compounds of formula I. A preferred method of working up includes: pouring the reaction mixture onto ice; extracting the compound of formula xcu; c-Eca wherein R R R A, B, E, F, X, Y, Y' and Z are as above.

I with a conventional inert organic solvent, preferably diethyl ether; washing the solvent extract with water;

drying the solvent and evaporating the solvent. The residual compound of formula I can be further purified by adsorption, preferably on Kieselgel or aluminum oxide.

The above reactions of a compound of formula II, wherein M is hydrogen, with an alkynyl halide of for mula Ill and of a compound of formula V, wherein M signifies hydrogen, with a compound of formula IV are expediently effected in the presence of an acid binding agent. in these reactions, any conventional acid binding agent may be utilized. The preferred acid binding agents are the carbonates and organic bases, such as pyridine, triethylamine and quinoline with the carbonates being especially preferred, particularly potassium carbonate. Further, in these reactions, wherein M of the compound of formula ll and M of the compound of formula V are hydrogen, the preferred solvents are acetone and methyl ethyl ketone.

Still another method for preparing the compounds of formula I, involves the esterification of an acid of the compound of formula VI where R is hydrogen with an alcohol of formula VI]. In carrying out this reaction, the acid is expediently converted, initially, in an inert solvent and in the presence of an acid binding agent into the corresponding acid halide by treatment with a halogenating agent. In this reaction, any conventional inert organic solvent can be used, with petroleum ether, benzene and hexane being preferred solvents. Also, in this reaction, any conventional acid binding agent, such as the organic bases, can be used, with pyridine, triethylamine, and quinoline being preferred and pyridine being especially preferred. Further, in this re action, any conventional halogenating agent such as thionyl chloride, phosphorus trichloride, thionyl brodiently effected in an excess of the alcohol, in which case this alcohol can also serve as the solvent. However, the reaction can also be conducted in an inert or ganic solvent, any conventional inert organic solvent 5 being suitable and the hydrocarbons, particularly benzene and toluene, being preferred. Temperature and pressure are not critical to this reaction, and the reaction can be expediently carried out in a temperature range between room temperature and the reflux tem l perature of the reaction mixture, with the reflux ter perature being preferred. This reaction is preferably carried out in the presence of a catalyst such as sodium, sodium methoxide, or ptoluenesulphonic acid,

The epoxidation of a compound of formula 1 wherein M is 1. Z is oxygen, and A and 8 taken together form a carbon to carbon bond can expediently be carried out by treating the compound in an inert solvent with a per acid. In carrying out this reaction, any conventional inert organic solvent may be utilized with the haloge nated hydrocarbons such as methylene chloride or chloroform being preferred. Any conventional peracid may be utilized in this reaction. Among the preferred peracids are perbenzoic acid, peracetic acid, pertungstic acid, performic acid, m-chloroperbenzoic acid and perphthalic acid, with m-chloroperbenzoic acid being especially preferred. ln carrying out this reaction, tem perature and pressure are not critical, the preferred temperature range being l0C. to room temperature. Another method for epoxidizing the compound of formula I, where M is I, wherein Z is oxygen or sulfur, and A and B taken together form a carbon to carbon bond, involves first treating the compound with water and an N-halosuccinimide, *halo" being chlorine, bro mine, or iodine, with N-bromosuccinimide being premide, and phosphorus oxychloride can be used, with fen-ed, t bt in a h lohydrin of the formula;

01-! l D VIII thionyl chloride being preferred. In this reaction, temperature and pressure are not critical, and the reaction may be suitably carried out at room temperature (25C).

The resulting acid halide and the alkynyl alcohol of formula Vll are then reacted in an inert solvent and in the presence of an acid binding agent, in this reaction, any conventional inert organic solvent can be utilized with benzene, toluene, hexane, iso-octane, chloroform, carbon tetrachloride and ethylene glycol dimethyl ether being preferred solvents. Also in this reaction, any conventional acid binding agent may be utilized, with the organic bases, such as pyridine, triethylamine and quinoline being preferred and pyridine being especially preferred, in carrying out this reaction, temperature and pressure are not critical, and the reaction can be suitably carried out at room temperature.

Still another method for preparing the compounds of formula 1 involves the trans-esterification of a compound of formula VI wherein R is alkyl or aralkyl utilizing an alcohol of formula Vll. This reaction is expewherein R,, R R R R R,,, C, D, E, F, X, Y, Y'

Z, n and p are as above, and Hal is chlorine, bromine or iodine.

in this reaction, temperature and pressure are not critical, the reaction being preferably carried out between 0 and 25C. In carrying out this reaction, the unsaturated compound of formula I is preferably intially suspended in water. Then an inert organic solvent is added to the suspension to give a homogeneous concentrated solution of the compound of formula I in water and organic solvent. Any conventional inert organic solvent can be utilized in this reaction, dioxane, tetrahydrofuran and l,2-dimethoxyethane being preferred. The N-halosuccinimide is then introduced portionwise into this homogeneous solution to yield the halohydrin of Vlll. Vllll.

These halohydrins can then be converted by the action of a base to the corresponding epoxide. in carrying out this reaction any conventional base is suitable, with the alkali metal alkanolatc being preferred, especially sodium methylate in methanol. In this reaction, temperature and pressure are not critical, the reaction manner with a metal hydride, such as an alkali metal being preferably carried out between 0 and 25C. Any hydride, in an inert organic solvent. in carrying out this conventional inert organic solvent can be utilized in reaction, any conventional metal hydride can be used, this reaction, dioxane, tetrahydrofuran and 1.2- with the preferred hydrides being mixed metal hydimethoxymethane being preferred. drides, particularly sodium borohydride or lithium alu- The compounds of formulas ll and VI can be obminum hydride, and alkylated metal hydrides, particutained by first reacting a compound of formula IV with larly, dialkyl aluminum hydrides. Especially preferred acompound of the formula: hydrides are di-isobutyl aluminum hydride and bis- (methoxy-ethyleneoxy) sodium aluminum hydride. ln

this reaction, any conventional, inert organic solvent IX can be used, with the preferred solvents being: the alkanols, especially methanol, in the presence of sodium borohydride, the ethers, especially tetrahydrofuran or dioxane, in the presence of lithium aluminum hydride;

l5 and the ethers and the hydrocarbons, especially hexwherein Z, M, Y and Y are as above; R is hydro ane, benzene or toluene, with the alkylated metal hygen, hydroxymethyl, formyl or COOR,,; and R is drides, particularly di-isobutyl aluminum hydride. Also, lower alkyl, aryl or aralkyl. in carrying out this reaction, temperature and pressure This reaction can be carried out in the same manner are not critical, with a temperature range of C. to described above for the reaction between the com- 20 50C. being preferred. pounds of formulas IV and V to yield a compound of The compound of formula X, wherein R is COOR the formula: can be converted to the compound of formula Xll,

wherein R, R R R R R A-F, Y, Y, Z, m, n wherein R,, is -COOH, by saponification. This saponiand p are as above. fication reaction can be carried out in a conventional The compound of formula X, wherein R, is formyl or manner using an alkali metal hydroxide, such as sodium COOR is then reduced to a compound of the foror potassium hydroxide. ln carrying out this reaction, mula: temperature and pressure are not critical. and the reac- \i/ Z Y'Y H F wherein R R R R R A-F, Y, Y, Z, m, n and tion can be carried out at elevated temperature. In this p are as above and R is CH OH. reaction, any conventional inert solvent which dis- Alternatively, the compound of formula X, wherein R solves both the alkali metal hydroxide and the comis --COOR is then saponified or the compound of forpound of formula X may be utilized with diethylene mula X, wherein R is formyl, is then oxidized to a com glycol/water or methanol/water l l being preferred. pound of the formula: The compound of formula X, wherein R is formyl,

r D l E l A E v l m n p R":

wherein R R R R R A-F, Y, Y', Z, m, n and can be converted to the compound of formula Xll, p are as above and R'Q, is COOH. wherein 11",, is COOH, by oxidation. This oxidation The compound of formula X, wherein R is formyl or reaction can be carried out in a conventional manner --COOR can be converted to the compound of forusing silver oxide. ln carrying out this reaction, temper mula Xl, wherein R,, is -CH,OH, by reduction. This ature and pressure are not critical, and the reaction can reduction reaction can be carried out in a conventional be carried out at room temperature. The silver oxide,

preferably Ag O, is preferably formed in situ in an aqueous solution of silver nitrate and caustic soda (NaOH). This reaction is carried out in water or in an organic solvent miscible with water. Any conventional organic solvent miscible with water may be used, with the following solvents being preferred: the lower alcohols, particularly methanol, ethanol and isopropanol', the ethers, particularly, l,4-dioxane; and the ether alcohols, particularly Z-methoxy-ethanol and Z-ethoxyethanol.

When the compounds of formulas X, X1, and Xll, wherein Z is oxygen, are unsaturated, they can, if desired, be hydrogenated in a conventional manner by, for example, hydrogenating in the presence of a conventional hydrogenation catalyst. in carrying out this reaction, temperature and pressure are not critical, a temperature range between about 25C. and the boiling temperature of the reaction mixture and atmospheric or elevated pressures being preferred. Suitable as hydrogenation catalysts are, for example, Raney-nickel or preferably the noble metals, with palladium and platinum being especially preferred. Suitable as solvents are acetic acid ethyl ester and the alkanols such as methanol and ethanol.

When the compounds of formulas X, XI, and Xll, are unsaturated, they can, if desired, be epoxidized in the same manner described above for the epoxidation of the compounds of formula l.

The compounds of formula X, wherein R is hydroxy or hydroxymethyl, of formula Xl wherein R is CH- H and of formula Xll, wherein R" is --COOH, can be directly converted to the alkali metal salt of formula ll. This reaction can be expediently effected by treatment with an alkali metal hydride, alkali metal alcoholate or an alkali metal hydroxide, sodium being the preferred alkali metal. This reaction is preferably carried out in the presence of an inert organic solvent. Any conventional inert organic solvent may be utilized, with dioxane, tetrahydrofuran, dimethylformamide or diethyl ether being the preferred solvents with an alkali metal hydride, with a lower alkanol, especially methanol, being the preferred solvent with an alkali metal alcoholate, and with methanol, ethanol, acetone or the like being the preferred solvent with an alkali metal hydroxide.

In the species of the compounds of formulas l, ll, IV, Vl, X, XI and Xll of this invention, wherein the sidechain is unsaturated or epoxidized, these species exist as a cis/trans isomer mixture. The isomer mixture can be separated into the all cis or all trans isomers in a conventional manner by, for example, gas chromatography.

By this method, the isomer mixture is dissolved in an inert organic solvent, hexane, diethyl ether or acetic acid ethyl ester being preferred solvents, and then adsorbed on Kieselgel. The isomers adsorbed in different zones can be eluted with one of the aforesaid solvents or solvent mixtures and isolated.

The isomer mixtures can, in individual cases, also be separated by fractional distillation methods or possibly also by fractional crystallization methods.

The following examples illustrate the invention. All temperatures are stated in degrees centrigrade. The inert gas atmosphere is nitrogen. The term hexane/l5 acetic ester" as used in Examples 5 and 41 encompasses a solution consisting of 85 7c hexane and 15 7c ethyl acetate (by volume). The tern 71 bis(2- methoxy-ethoxy) sodium aluminium hydride" as used in Example 27 comprehends a benzenic solution of 70 by weight of bis(2-methoxy-ethoxy )sodium aluminium hydride. The term 7: by weight mchlorperbenzoic acid" as used in Examples 31, 33 and 34 means that the m-chlorperbenzoic acid contains 20 m-chlorbenzoic acid and that the percentage of mchlorperbenzoic acid present in the mixture was determined by titration in the usual manner.

EXAMPLE 1 l l.8 g of a 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with 50 ml of tetrahydrofuran each time and then added to 150 ml of tetrahydrofuran. A solution of 36.5 g of hydroquinone monopropargyl ether dissolved in 80 ml of tetrahydrofuran is then added dropwise to the sodium hydride mixture. 47.5 g of 2-bromo-6- methylheptane in 80 ml of hexamethyl phosphoric acid triamide is subsequently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual, oily, l-[( l ,S-dimethylhexyl)oxyl-4-propargyloxy benzene is purified by adsorption on Kieselgel; B.P. l50l52C/l mmHg.

EXAMPLE 2 By utilizing the procedure of Example I, by reacting hydroquinone monopropargyl ether with 3-methyl-2- butenyl bromide, there is obtained l-[(3-methyl-2- butenyl)oxy]-4-propargyloxy-benzene; B.P. l45-148C/l mml-lg.

EXAMPLE 3 By utilizing the procedure of Example I by reacting syringic acid propargyl ester with geranyl bromide, there is obtained 4-[(3,7dimethyl-2,6-octadienyl)oxy]-3,5-dimethoxy benzoic acid propargyl ester; n 1.5320

EXAMPLE 4 By utilizing the procedure of Example 1, by reacting S-bromo-vanillic acid propargyl ester and geranyl bromide, there is obtained 3-bromo-4-[(6,7-dimethyl-2,6- octadienyl)oxy]-5-methoxy-benzoic acid propargyl ester; n 1.5440.

EXAMPLE 5 43.5 g of a 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with l00 ml of tetrahydrofuran each time and then, added to I50 ml of tetrahydrofuran. A solution of I00 g of hydroquinone in ml of tetrahydrofuran is added dropwise to the sodium hydride mixture. I08 g of propargyl bromide in ml of hexamethyl phosphoric acid triamide is subsequently added drop wise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual mixture is separated by chromatography on Kieselgel. Hydroquinone dipropargyl ether is eluted with 10% acetic ester. M.P. 50C. With hexane/l57z acetic ester there is eluted hydroquinone monopropargyl ether. B.P. l-102C/1.0 mml-lg.

EXAMPLE 6 By utilizing the procedure of Example 5, by reacting syringic acid and propargyl bromide, there is obtained syringic acid propargyl ester, F. P. 105-106C.

EXAMPLE 7 By utilizing the procedure of Example 5, by reacting -bromovanil1ic acid with propargyl bromide, there is obtained S-bromovanillic acid propargyl ester; M.P. l2l-l22C.

EXAMPLE 8 4.0 g of a 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with 25 ml of tetrahydrofuran each time and then, added to 100 ml of tetrahydrofuran. A solution of 20.6 g of p-[( 1,S-dimethylhexyl)oxy]benzoic acid in 100 ml of tetrahydrofuran is then added dropwise to the sodium hydride mixture. g of propargyl bromide in 40 ml of hexamethyl phosphoric acid triamide is subsequently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual oily p-[( 1,5- dimethylhexyl)oxylbenzoic acid propargyl ester is purified by adsorption of Kieselgel', B.P. 2072l0C/1 mmHg.

EXAMPLE 9 By utilizing the procedure of Example 8, by reacting p-farnesyloxybenzoic acid with propargyl bromide, there is obtained p-farnesyloxybenzoic acid propargyl ester; B.P. 245250C/0.1 mmHg.

EXAMPLE 10 By utilizing the procedure of Example 8, by reacting p-[( l ,5-dimethyl-4-hexenyl )oxylbenzoic acid with propargyl bromide, there is obtained p-[(1,5-dimethyl-4- hexenyl)oxy]benzoic acid propargyl ester; n 1.5252.

EXAMPLE 11 By utilizing the procedure of Example 8, by reacting p-[( 3,7-dimethyl-2,o-octadienyl)oxylbenzoic acid with propargyl bromide, there is obtained p-[(3,7-dimethy1- 2,6-octadienyl)oxy]benzoic acid propargyl ester; B.P. l35137C/0.01 mmHg.

EXAMPLE 12 By utilizing the procedure of Example 8, by reacting p-[ 3,6,7-trimethylocta-2,o-dienyl )oxy ]benzoic acid with propargyl bromide, there is obtained p-[(3,6,7- trimethylocta-2,6-dienyl)oxy]benzoic acid propargyl ester; 11,," 1.5349.

EXAMPLE 13 By utilizing the procedure of Example 8, by reacting P-H1,S-dimethylhexyl)oxyl-3-chlorobenzoic acid with propargyl bromide, there is obtained 4-[(1,5- dimethylhexyl)oxy]-3-chlorobenzoic acid propargyl ester; n 1.5155.

EXAMPLE l4 By utilizing the procedure of Example 8, by reacting p-[( 1,5-dimethylhexy1)oxy]vanillic acid with propargyl bromide, there is obtained p-[(l,5-dimethylhexyl)oxylvanillic acid propargyl ester; n 1.5151.

EXAMPLE [5 By utilizing the procedure of Example 8, by reacting p-[(l,4,5-trimethylhexyl)oxy]benzoic acid with propargyl bromide, there is obtained p-[(l,4,5- trimethylhexyl)oxy]benzoic acid propargyl ester; n

EXAMPLE 16 By utilizing the procedure of Example 8, by reacting p-[( l,S-dimethylhexyl)oxylbenzoic acid with l-bromo- 2-pentyne, there is obtained p-[(1,5-dimethylhexyl)oxylbenzoic acid-Z-pentynyl ester; n 1.5078.

EXAMPLE 17 By utilizing the procedure of Example 8, by reacting p-[( l-ethyl 5 methyl-4-heptenyl )oxy ]benzoic acid with propargyl bromide, there is obtained p-[( l-ethyl- 5-methyl-4-heptenyl)oxy]benzoic acid propargyl ester; 11,," 1.5200.

EXAMPLE 18 By utilizing the procedure of Example 8, by reacting 3-methyl-4-[(3,7-dimethylocta-2,fi-octadienyl)-oxy]- benzoic acid with propargyl bromide, there is obtained 3-methyl-4-[ 3,7-dimethylocta-2,6-dienyl )oxy ]benzoic acid propargyl ester; m, 1.5331.

EXAMPLE 19 13.7 g of a 50% suspension ofsodium hydride in mineral oil is washed twice in an inert gas atmosphere with ml of tetrahydrofuran each time and then, added to 100 ml of tetrahydrofuran. A solution of 40 g of phydroxybenzoic acid methyl ester in 250 ml of tetrahydrofuran is then added dropwise to the sodium hydride mixture. 50 g of 2-bromo-6-methylhept-5-ene in ml of hexamethylphosphoric acid triamide is subsequently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual oily p-[( 1,5-dimethy1-4-hexenyl)oxy]benzoic acid methyl ester is purified by adsorption on Kieselgel; n 1.5109.

EXAMPLE 20 By utilizing the procedure of Example 19. by reacting p-hydroxybenzoic acid methyl ester with 2-bromo-6- methyl heptane, there is obtained p-[(l,5- dimethylhexyl)oxy]benzoic acid methyl ester; B.P. 132l34C/.l mmHg.

EXAMPLE 21 By utilizing the procedure of Example 19, by reacting p-hydroxybenzoic acid methyl ester with 2-bromo-5,6- dirnethyl heptane, there is obtained p-[(1,4,5 trimethylhexyl)oxy]benzoic acid methyl ester; n 1.4938.

EXAMPLE 22 By utilizing the procedure of Example l9, by reacting p-hydroxybenzoic acid methyl ester with 3-bromo-7- methylnon--ene, there is obtained p-[( l-ethyl-5 methyl-4-haptenyl)oxylbenzoic acid methyl ester; B.P. 202-205C/l2 mmHg.

EXAMPLE 23 By utilizing the procedure of Example 19, by reacting 3-methyl-4-hydroxybenzoic acid methyl ester with 1- bromo-3,7-dimethyl-2,6-octadiene, there is obtained 3-methyl-4-[( 3,7-dimethyl-2,o-octadienyl )oxy ]benzoic acid methyl ester; n l.5248.

EXAMPLE 24 7.2 g of p-[(l,5-dimethyl-hex-4-enyl)oxy]-benzoic acid methyl ester is dissolved in 30 ml of 2-N aqueous caustic soda, diluted with 50 ml of an aqueous solution of 50% by volume methanol and heated under reflux for 1 /2 hours. The reaction solution is then cooled, treated with 200 ml of water and exhaustively extracted with diethyl ether. The alkaline aqueous phase is aciditied with 2-N hydrochloric acid and exhaustively extracted with diethyl ether. The latter ether extract is dried over sodium sulfate and evaporated under reduced pressure. The residual p-[( 1,5-dimethyl-hex-4- enyl)oxy]benzoic acid is purified by crystallization from benzene; M.P. 57-59C.

EXAMPLE 25 acid;

p-[( l ,S-dimethylhexyl)oxyl-3-chlorobenzoic acid;

p-[( l,5dimethylhexyl)oxylvanillic acid; M.P.

p-l(l,4.S-trimethylhexyl)oxylbenzoic acid; n

p l-ethyl-5-methyl-4-heptenyi)oxy]benzoic acid;

n 1.4891; and 3-methyl-4-[( 3,7-dimethyl-2,o-octadienyl )oxy lbenzoic acid; F.P. 9394C.

EXAMPLE 26 4.1 g of a 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with 25 ml of tetrahydrofuran each time and then, added to 50 ml of tetrahydrofuran. A solution of 20 g of p-[(l,S-dimethylhexyl)oxy]benzyl alcohol in I00 ml of tetrahydrofuran is then added dropwise to this mixture. l0.3 g propargyl bromide in 40 ml of he amethyl phosphoric acid triamide is subseqently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual oily p-[( [,5-

dimethylhexyl)oxyl-wpropargyloxytoluene is purified by adsorption on Kieselgel; B.P. l-l75C/l.0 mmHg.

EXAMPLE 27 42 g of p-[( l,S-dimethylhexyl)oxylbenzoic acid methyl ester is dissolved in 250 ml of benzene and, with stirring, treated dropwise with 50 g of 70% bis(2-methoxy-ethoxy)sodium aluminum hydride. The reaction solution is further stirred at 25C. for 5 hours and thereafter treated with water. The organic phase is separated off. dried under sodium sulfte. carefully fil tered (using a filter aid) and evaporated under reduced pressure. There is obtained a residual of p-[( 1,5- dimethylhexyl)oxy]benzyl alcohol; B.P. l-l82C/l.0 mmHg.

EXAMPLE 28 By utilizing the procedure of Example 26, by reaction p-l(3-methyl-2-butenyl)oxy]benzyl alcohol with propargyl bromide, there is obtained p-[(3-methyl-2- butenyl)oxyl-2-proparagyloxytoluene; B.P. l46-l49C/l mmHg.

EXAMPLE 29 [0.] g of a 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with 50 ml of tetrahydrofuran each time and then, introduced into ml of tetrahydrofuran. A solution of 32 g of p-hydroxybenzoic acid methyl ester in 200 ml of tetrahydrofuran is then added dropwise to the sodium hydride mixture. 405 g of l-bromo-3- methylbut-Z-ene in 80 ml of hexamethyl phosphoric acid triamide is subsequently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual oily p-[(3-methyl-2-butenyl)oxy]benzoic acid methyl ester is purified by adsorption on Kieselgel. M.P. 45-46C.

By utilizing the procedure of Example 27, p-[(3- methyI-Z-butenyl )oxylbenzoic acid methyl ester is converted into p-[t3-methyl-2-butenyl)oxylbenzyl alcohol; M.P. 4l-42C.

EXAMPLE 30 2,2 g of 50% by weight suspension of sodium hydride in mineral oil is washed twice in an inert gas atmosphere with 25 ml of tetrahydrofuran each time and then added to 30 ml of tetrahydrofuran a solution of 9.9 g of p-[(2,3-epoxy-3-methylbutyl)oxylbenzoic acid in 100 ml of tetrahydrofuran is then added dropwise to the sodium hydride mixture 5.5 g of propargyl bromide in 20 ml of hexamethyl phosphoric acid triamide is subsequently added dropwise to the mixture. The reaction mixture is heated under reflux conditions for 2 hours, then cooled, poured onto ice and exhaustively extracted with diethyl ether. The ether extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residual oily p-[(2,3- epoxy-3-methylbutyl)oxy]benzoic acid propargyl ester is purified by adsorption on Kieselgel; M.P. 808lC.

EXAMPLE 3| 3.9 g of P-[(1,5-dimethyl-hex-4-enyl)oxylbenzoic acid propargyl ester is dissolved in ml of methylene chloride. The solution is treated dropwise at C. with a solution of 3.0 g of 80% by weight mchloroperbenzoic acid in l00 ml of methylene chloride. After mins., the reaction mixture is successively washed with an aqueous solution of 2% by weight sodium bisulphite with an aqueous solution of 5% by weight sodium bicarbonate and with water. The organic phase is separated off, washed over sodium sulphate and evaporated under reduced pressure. The residual p-[(4,5-epoxy-l,S-dimethylhexy)oxy1benzoic acid propargyl ester is purified by absorption on Kieselgel; B.P. ll23C/0.05 mmHg.

EXAMPLE 32 By utilizing the procedure of Example 31. 2.0 g of p- [(3,7-dimethyl-2.6-octadienyl)oxy]benzoic acid propargyl ester is converted into P-((6,7-epoxy-3,7- dimethyl-Z-octenyl)oxylbenzoic acid propargyl ester; n,, 1.5362.

EXAMPLE 33 EXAMPLE 34 6.4 g of l-[ 3-methyl-2-butenyl )oxy]-4- propargyloxy-benzene is dissolved in 80 ml of methylenechloride and cooled to 0C. (ice-bath cooling). 7. l 5 g of 80% by weight m-chloroperbenzoic acid is added portionwise to this mixture and the solution is thereafter stirred at 0C. for 2 hours. The mixture is worked up as follows: diluted with 350 ml of methylene chloride; washed with ice-cold l-N caustic soda; washed with saturated aqueous sodium chloride solution; dried over sodium sulfate; and evaporated. By chromatography on Kieselgel. there is obtained l-{(2,3-epoxy-3- methylbutyl)oxy]-4-propargyloxy-benzene; M.P. 7273C.

EXAMPLE 35 By utilizing the procedure of Example 26, by reacting p-[(l,S-dimethylhexyl)thio]benzyl alcohol with propargyl bromide, there is obtained p-[(l,5- dimethylhexyl)thio]-a-propargyloxy-toluene; m, 1.5243.

EXAMPLE 36 By utilizing the procedure of Example 27. p-[( l,5- dimethylhexyl)thio]benzoic acid methyl ester is converted into p-[( l.5-dimethylhexyl)thio]benzyl alcohol; n f" 1.5270.

EXAMPLE 37 By utilizing the procedure of Example 19, by reacting p-thio benzoic acid methyl ester with 2-bromo-6- methylheptane. there is obtained p-[( l ,5-

18 dimethylhexyl)-thio]benzoic acid methyl ester; B.P. l68-l70C/0.5 mmHg.

EXAMPLE 38 By utilizing the procedure of Example 8. by reacting p-[{ l,S-dimethylhexyl)thiolbenzoic acid and propargyl bromide, there is obtained p-[(l.5-dimethylhexyl)thio]benzoic acid propargyl ester M.P. l30l3lC/0.03 mmHg.

EXAMPLE 39 By utilizing the procedure of Example 24, p-[( i5- dimethyl-hexyl)thiolbenzoic acid methyl ester is converted into p-[(l,5-dimethylhexyl)thiolbenzoic acid; M.P. 63-65C.

EXAMPLE 40 By utilizing the procedure of Example 8. by reacting p-[(3 6, 7-trimethyloctyl)oxylbenzoic acid with propargyl bromide there is obtained p-[3.6,7- trimethyloctyl)oxy]benzoic acid propargyl ester; B.P. l53l54C/0.05 mmHg.

EXAMPLE 4] 5 g of p-[(3 6.7-trimethylocta-2.6-dienyl)oxylbenzoic acid is dissolved in 20 ml of acetic ester and hydrogenated under normal pressure and at a temperature of about 25C. in the presence of 0.2 of platinum oxide. The hydrogenation is terminated after the uptake of 2 mols of hydrogen, and the catalyst is filtered off from the reaction mixture. The clear solution is evaporated under reduced pressure. The residual p-[(3.6,7-trimethyloctyl)oxyl]benzoic acid is purified by crystalliza tion from petroleum ether; M.P. 8990C.

EXAMPLE 42 10 g of p-[(l.S-dimethylhexyl)oxylbenzoic acid is heated to C. with 20 ml of thionyl chloride for l0 mins. The clear yellow-colored solution is evaporated at 50C. under water-jet pump vacuum. After the addition of 40 ml of propargyl alcohol. the mixture is heated to 70C for 15 min. After evaporation in waterjet pump vacuum, the residue is chromatographed on Kieselgel yielding P-[(l,S-dimethylhexyl)oxylbenzoic acid propargyl ester; B.P. 2072l0C/l.0 mmHg.

EXAMPLE 43 10 g of p-[( l,S-dimethylhexyl)oxylbenzoic acid methyl ester, 30 ml of propargyl alcohol and 0.5 of sodium methoxide are heated to reflux for one-half an hour. The excess propargyl alcohol is thereupon slowly {5 hrs.) distilled off. The residue is poured onto water and extracted with diethyl ether. The ether solution is dried with sodium sulfate and evaporated. The darkyellow p-[( l,S-dimethylhexyl)oxy]benzoic acid propargyl ester obtained is purified over Kieselgel.

EXAMPLE 44 13 g of p-[( l ,5-dirnethyhexyl)oxy]benzoic acid methyl ester is heated to reflux with 9 g of propargyl alcohol and 0.l g of p-toluenesulphonic acid. The excess propargyl alcohol is thereupon slowly (5 hrs.) distilled off. The residue is poured onto water and extracted with diethyl ether. The ether phase is dried with sodium sulfate and evaporated. There is obtained dark-yellow p-[(l,S-dimethylhexyl)oxylbenzoic acid propargyl ester which is purified on Kieselgel.

EXAMPLE 45 2 filter paper discs [24 cm are sprayed with an acetonic solution of the active substance and after drying the discs together with an untreated paper disc and with a paper disc soaked only with acetone. are each so fixed together that there is formed a tunnel for the shelter of cockroaches (Blane/la germanica) each. The cockroaches are in the last larval stage. They remain in permanent contact with the treated paper and germanica) provided with water and food.

The development of the larvae set out is registered daily. 100% disturbance of metamorphosis: A normal acid animal develops from none of the larvae Aethe Amount of Num Num- Number Activity her her subactive of of of 7r stance substance larvae normal normal ll)"glcm'-' images animals I It)" If] I 5 83 Control with acetone Ill [0 Control with acetone It] lll EXAMPLE 46 A disc of cotton material l0 cm' is sprayed with an acetonic solution of the active substance, and after dry ing, the disc, together with an untreated disc of material and a disc of material soaked only with acetone, are each occupied by 30-60 freshly laid eggs of the meal moth (Eplieslia kiihniella). The disc is placed in a cage and held at C. and 90% rel. humidity.

The development of the eggs is registered over a few days. l00% mortality of the eggs: No development of the embryos in the eggs layed on discs of material soaked with active substance.

Active Amount of Number of Number of EXAMPLE 47 A disc of woollen material [10 cm l is sprayed with an acetonic solution of the active substance, and the disc. together with an untreated disc of material and a disc of material soaked only with acetone, are each hung in a cage occupied by 20 young cloths moth Tineuia hiselliellu The development of the eggs layed at 25C. is regis tcred for 4 days. lOO7z sterilant action: larvae hatch from none of the eggs laid on treated and untreated discs of woolen material. l00% ovicidal action: larvae hatch from none of the eggs laid on treated discs of woollen material.

Actiw substance Amount of Stcrilant Ovicidal active action action substance ltl gi cm Vl ltl 0 I00 10 i (J 100 Control with acetone 0 0 Control with acetone 0 EXAMPLE 48 A filter paper strip {90 cm*] is sprayed with an ace tonic solution of the active substance and, after drying. the strip, together with an untreated paper strip and a paper strip soaked only with acetone, are each occupied by 3-4 pairs of freshly moulted images of the cotton bug (Dysa'ercus cingulatus).

The development of the eggs laid daily is registered. 100% mortality of the eggs: no development of the embryos in the eggs laid on strips soaked with active substance.

propynyloxy)toluene was dissolved in a mixture of ml of dioxane and 40 ml of water. To this solution there was added under cooling with ice (lOC) portionwise 0.85 g of N-bromosuccinimide. After this addition the mixture was stirred at room temperature for 15 hours and then diluted with 80 ml of water. Thereafter 2.5 g of sodium sulfite are added and the solution exhaustively extracted with ether. The combined ether extracts were washed with water. dried over sodium sulfate and evaporated. By chromatography on Kieselgel with hexane/ethyl acetate l5 parts by volume) there was obtained p-[(3-bromo-2-hydroxy-3- methylbutyl)oxy]-a-(2-propynyloxy)toluene. a 1.5374

We claim: 1. A compound of the formula:

wherein R R and R, are methyl or ethyl; R, and R wherein R h R R A, B Z, Y, Y and X are as above. 3. The compound of claim 2 wherein A and B taken together are a carbon to carbon bond.

4. The compound of claim 1 wherein X is oxygen. 5. The compound of claim 4 wherein said compound I Hi I is l-[(l,S-dimethylhexyl)-oxy]-4-(propargyloxy) ben are hydrogen or methyl; R is propargyl A, B, C, D, zene.

E and F are individually hydrogen or A and 8 taken 6. The compound of claim 2 wherein Y is lower alkyl. together form a carbon to carbon bond C and D 7. The compound of claim 2 wherein Y is lower taken together form a carbon to carbon bond, and alkexy. E and F taken together form a carbon to carbon 8. The compound of claim 2 wherein Y is a halogen. bond; Z is oxygen Y and Y are hydrogen, halogen, 9. The compound of claim I having the formula:

lower alkyl or lower alkoxy; X is oxygen or CH- wherein R R R A, B, E, F, Y, Y Z and X are as above. l0. The compound of claim 9 wherein E and F are a O; and m, n and p are intergers of from 0 to l, with at least one of m, n and p being I with the proviso that when m and n are 0, E and F are individub n to carbon bond. y hydrogenor lake" together form a Carbon to 11. The compound of claim 9 wherein A and B taken Carbon bondtogether are a carbon to carbon bond and E and F 2. The compound of claim 1 having the formula: taken together are a carbon to carbon bond.

12. The compound of claim 1 wherein X is CH- F Rs 0.

B 13. The compound of claim 12 wherein said comi Y 40 pound is p-[( l,5-dimethylhexyl)oxy]-apropargyloxytoluene. A 14. The compound of claim 12 wherein said com- Re i pound is p-[(3-methyl-2-butenyl)oxyl-a- X--CH .-CECH propargyloxytoluene.

15. The compound of claim 4 wherein said compound is l-[(3-methyl-2-butenyl)oxy]-4- propargyloxybenzene. 

1. A COMPOUNND OF THE FORMULA:
 2. The compound of claim 1 having the formula:
 3. The compound of claim 2 wherein A and B taken together are a carbon to carbon bond.
 4. The compound of claim 1 wherein X is oxygen.
 5. The compound of claim 4 wherein said compound is 1-((1,5-dimethylhexyl)-oxy)-4-(propargyloxy) benzene.
 6. The compound of claim 2 wherein Y is lower alkyl.
 7. The compound of claim 2 wherein Y is lower alkexy.
 8. The compound of claim 2 wherein Y is a halogen.
 9. The compound of claim 1 having the formula:
 10. The compound of claim 9 wherein E and F are a carbon to carbon bond.
 11. The compound of claim 9 wherein A and B taken together are a carbon to carbon bond and E and F taken together are a carbon to carbon bond.
 12. The compound of claim 1 wherein X is -CH2O-.
 13. The compound of claim 12 wherein said compound is p-((1,5-dimethylhexyl)oxy)- Alpha -propargyloxytoluene.
 14. The compound of claim 12 wherein said compound is p-((3-methyl-2-butenyl)oxy)- Alpha -propargyloxytoluenE.
 15. The compound of claim 4 wherein said compound is 1-((3-methyl-2-butenyl)oxy)-4-propargyloxybenzene. 